CN108855194A - A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity and preparation method thereof - Google Patents
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 37
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 238000000889 atomisation Methods 0.000 claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 238000010891 electric arc Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 229940073609 bismuth oxychloride Drugs 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of nitrogen-doped nanometer BiOX type photochemical catalyst and preparation method thereof of high catalytic activity, is related to photocatalysis technology field, and molecular formula is (BiOX)1‑YNY, X Cl, Br, I any one, Y 0.25-0.35%, preparation method includes the following steps：By refined bismuth heating melting, it is passed through nitrogen, continues heating and obtains superheated melt；Atomization is broken to obtain ultra-fine bead, burns, obtains liquid Bi2O3；It is added in excess HX, ammonium hydroxide is added dropwise, obtains BiOX colloid；Prepare BiOX gel；Carry out N doping reaction, reaction time is 10-15min, reaction terminates that nitrogen-doped nanometer BiOX type photochemical catalyst can be obtained, after N doping, due to the introducing of impurity state, cause there is new impurity energy level to generate between band gap step, the energy band number of plies accordingly increases, these impurity energy levels are as intermediate level, effectively electronics can be assisted to transit to conduction band from valence band, to improve electron mobility, impurity energy level can capture electronics, the separation rate for improving electrons and holes, improves the catalytic activity of photochemical catalyst.
Description
Technical field
The present invention relates to photocatalysis technology fields, and in particular to a kind of nitrogen-doped nanometer BiOX type light of high catalytic activity is urged
Agent and preparation method thereof.
Background technique
Photocatalysis technology can directly convert solar energy into chemical energy and electric energy by conductor photocatalysis material, and can
Permineralization degradation is realized to organic pollutant poisonous and harmful in environment,
Its principle is using semiconductor as catalyst, and the energy band that semiconductor is occupied by valence electron claims valence band, adjacent that
A higher energy band, that is, excitation state is known as conduction band, and there are forbidden bands between valence band and energy band, when the light for being greater than forbidden bandwidth with energy
When irradiation, the photoelectron that energy is greater than forbidden bandwidth is absorbed, by the electron excitation of valence band to conduction band, with electricity in conduction band
Son generates hole in valence band, and electronics has reproducibility, and hole has oxidisability, and hole has the extremely strong energy for obtaining electronics
Power, can be by the OH- and H in water2O is oxidized to the OH free radical with strong oxidizing property, and OH free radical is with 402MJ/mol's
Reaction energy, can destroy C-C, C-H, C-O, C-N, N-H key in organic matter, many oxidation operations difficult to degrade are become
CO2And H2The inorganic matters such as O, it is considered as the current solution most potential technical solution of human society energy and environmental problem
One of.
Fujishima is put forward for the first time the concept of photochemical catalytic oxidation within 1972, has attracted from chemistry, physics, material, energy
The extensive concern of the various aspects scholar such as source, environment.Wherein, (photocatalytic activity and expansion are improved to the study on the modification of photochemical catalyst
The absorption region of light), especially modification by ion-doping is studied, and has become the focus of vast focus of attention.
In recent years, domestic and foreign scholars had developed many novel photocatalysis materials, and such as lamellar compound constructs type novel compounds
Object, metal hydroxides, multi-element metal oxide etc., wherein representative oxyhalogen bismuth system BiOX (X in lamellar compound
=Cl, Br, I) catalysis material, especially BiOCl semiconductor material, show unique layer structure, characteristic electron, optics
Property and good photocatalytic activity and stability cause the very big concern of the domestic and international scientist of photocatalysis field, to its into
The research of row doping vario-property, improving its photocatalytic activity is one of the development projects with very high potential in following a period of time.
The patent that application notification number is 106984338 A of CN, which discloses, a kind of prepares semiconductor using industrial wastewater
Five water bismuth nitrates are added into industrial wastewater the method for BiOxCly type photochemical catalyst, in the ultrasonic machine that power is 100Hz
Ultrasound simultaneously stirs 30min, is dispersed in five water bismuth nitrates in industrial wastewater, then by industrial wastewater and five water bismuth nitrates
Mixed solution is fully transferred in reaction kettle, is placed in homogeneous reactor again after tightening reaction kettle, is added under the conditions of certain temperature
The semiconductor BiOxCly type photochemical catalyst of hot preparation highlight catalytic active.Prepared semiconductor BiOxCly type photochemical catalyst exists
Photocatalytic activity under ultraviolet light is significantly higher than P25 type titanium dioxide and the light of bismuth oxychloride semiconductor light-catalyst is urged
Change activity；During preparing semiconductor BiOxCly type photochemical catalyst, significantly reduces the COD in waste water, sodium chloride etc. and be difficult to
The pollutant of processing, while total phosphorus is largely converted to orthophosphates, photocatalytic activity can also be by doping vario-properties into one
Step improves, to improve the processing capacity to sewage.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of nitrogen-doped nanometer BiOX type photocatalysis of high catalytic activity
Agent and preparation method thereof.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, molecular formula are (BiOX)1-YNY, X Cl,
Br, I any one, Y 0.25-0.35%.
The preparation method of the nitrogen-doped nanometer BiOX type photochemical catalyst of above-mentioned high catalytic activity, includes the following steps：
(1) refined bismuth is heated to 280-300 DEG C of melting and obtains melt, it is continual into melt to be passed through nitrogen, heat preservation
After stirring 20-50min, continue to be heated to 860-950 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by diversion pipe, it is thin using atomization gas continuous crushing superheated melt
Stream, obtains ultra-fine bead, ultra-fine bead burns in oxygen, obtains liquid Bi2O3；
(3) by liquid Bi under 600-800r/min high-speed stirred2O3It is added in 60-80 DEG C of excessive HX, is clarified
After solution, ammonium hydroxide is added dropwise, stirs 20-40min, reduces revolving speed to 400r/min, continues to stir 20-40min, finally reduce and turn
To 100r/min, natural cooling cools down speed at this time, obtains BiOX colloid；
(4) BiOX colloid is centrifugated 10-20min, the solid material being centrifuged with the speed of 4000-6000r/min
It is respectively washed 3 times with distilled water and dehydrated alcohol；
(5) under conditions of pressure 8-10MPa, 35 DEG C of temperature, carbon dioxide flow 5-10m/s, dehydrated alcohol is replaced
For liquid carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOX gel；
(6) BiOX gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 10-15min, and reaction terminates that nitrogen-doped nanometer BiOX type light can be obtained
Catalyst.
Further, the flow velocity of the nitrogen is 2-5m/s.
Further, the diameter of the diversion pipe is 1-4mm.
Further, the atomization gas is air, nitrogen, any one in argon gas.
Further, the flow velocity of the atomization gas is 60-100m/s.
Further, the temperature of the atomization gas is 80-100 DEG C.
Further, the HX be HCl, HBr, HI any one.
Further, the ammoniacal liquor mass concentration is 15-25%.
(3) beneficial effect
The present invention provides nitrogen-doped nanometer BiOX type photochemical catalysts of a kind of high catalytic activity and preparation method thereof, have
Following beneficial effect：
BiOX belongs to tetragonal crystalline structure, double X in crystal-Sheath and [Bi2O2]2+Layer is alternately arranged composition layer structure,
It is combined by non-bonding force, short texture, it is intermediate there are an electrostatic subfield, facilitate photoelectron-hole to efficiently separating, and
And since Cl, Br and I belong to congeners, rejection is small, in addition the respective band gap of BiOCl, BiOBr, BiOI (3.40eV,
2.92eV, 1.85eV) it is more moderate, certain band gap step can be formed, it is ensured that absorb the solar energy of different-waveband, BiOX warp
After crossing N doping, due to the introducing of impurity state, cause there is new impurity energy level to generate between band gap step, the one side energy band number of plies
Accordingly increase, become finer and close, these impurity energy levels effectively can assist electronics to transit to from valence band as intermediate level
Conduction band, to improve electron mobility, another aspect impurity energy level can be used as shallow donor's energy level, captures electronics, extends light
The recombination time of raw electronics and hole, the separation rate of electrons and holes is improved, the catalytic activity of photochemical catalyst is improved.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.28%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 280 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 4m/s into melt is protected
After temperature stirring 40min, continue to be heated to 870 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 2mm, is 80m/s, temperature using flow velocity
For 85 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 700r/min high-speed stirred2O3It is added in 65 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 20% is added dropwise, stirs 30min, reduces revolving speed to 400r/min, continues to stir 20min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOCl colloid for the slow-speed of revolution；
(4) above-mentioned BiOCl colloid is centrifugated 15min with the speed of 4000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8.5MPa, 35 DEG C of temperature, carbon dioxide flow 5m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 10min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Embodiment 2：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOBr)1- YNY, Y 0.25%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 290 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 50min, continue to be heated to 900 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 2mm, is 80m/s, temperature using flow velocity
For 90 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 700r/min high-speed stirred2O3It is added in 65 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 23% is added dropwise, stirs 25min, reduces revolving speed to 400r/min, continues to stir 30min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOBr colloid for the slow-speed of revolution；
(4) above-mentioned BiOBr colloid is centrifugated 15min with the speed of 4500r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8.5MPa, 35 DEG C of temperature, carbon dioxide flow 8m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOBr gel；
(6) BiOBr gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 12min, and reaction end can be obtained nitrogen-doped nanometer BiOBr type light and urge
Agent.
Embodiment 3：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOI)1- YNY, Y 0.33%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 50min, continue to be heated to 920 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 4mm, is 90m/s, temperature using flow velocity
For 100 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 750r/min high-speed stirred2O3It is added in 75 DEG C of excessive HI, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 25% is added dropwise, stirs 40min, reduces revolving speed to 400r/min, continues to stir 40min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOI colloid for the slow-speed of revolution；
(4) above-mentioned BiOI colloid is centrifugated 20min with the speed of 6000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 9MPa, 35 DEG C of temperature, carbon dioxide flow 8m/s, dehydrated alcohol is replaced into liquid
Carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOI gel；
(6) BiOI gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 15min, and reaction end can be obtained nitrogen-doped nanometer BiOI type light and urge
Agent.
Embodiment 4：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.35%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 280 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 2m/s into melt is protected
After temperature stirring 20min, continue to be heated to 860 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 1mm, is 60m/s, temperature using flow velocity
For 80 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 600r/min high-speed stirred2O3It is added in 60 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 15% is added dropwise, stirs 20min, reduces revolving speed to 400r/min, continues to stir 20min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOCl colloid for the slow-speed of revolution；
(4) above-mentioned BiOCl colloid is centrifugated 10min with the speed of 4000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8MPa, 35 DEG C of temperature, carbon dioxide flow 5m/s, dehydrated alcohol is replaced into liquid
Carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 10min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Embodiment 5：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.30%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 50min, continue to be heated to 950 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 4mm, is 100m/s, temperature using flow velocity
The nitrogen continuous crushing superheated melt thread that degree is 100 DEG C, obtains ultra-fine bead, ultra-fine bead burns in oxygen, obtains liquid
State Bi2O3；
(3) by liquid Bi under 800r/min high-speed stirred2O3It is added in 80 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 25% is added dropwise, stirs 40min, reduces revolving speed to 400r/min, continues to stir 40min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOCl colloid for the slow-speed of revolution；
(4) above-mentioned BiOCl colloid is centrifugated 20min with the speed of 6000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 10MPa, 35 DEG C of temperature, carbon dioxide flow 10m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 15min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Embodiment 6：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOBr)1- YNY, Y 0.25%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 40min, continue to be heated to 870 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 3mm, is 85m/s, temperature using flow velocity
For 95 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 600r/min high-speed stirred2O3It is added in 70 DEG C of excessive HBr, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 18% is added dropwise, stirs 40min, reduces revolving speed to 400r/min, continues to stir 30min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOBr colloid for the slow-speed of revolution；
(4) above-mentioned BiOBr colloid is centrifugated 12min with the speed of 5500r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8.5MPa, 35 DEG C of temperature, carbon dioxide flow 9m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOBr gel；
(6) BiOBr gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 13min, and reaction end can be obtained nitrogen-doped nanometer BiOBr type light and urge
Agent.
Embodiment 7：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.32%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 2m/s into melt is protected
After temperature stirring 50min, continue to be heated to 860 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 1mm, is 60m/s, temperature using flow velocity
For 100 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 600r/min high-speed stirred2O3It is added in 80 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 15% is added dropwise, stirs 20min, reduces revolving speed to 400r/min, continues to stir 40min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOCl colloid for the slow-speed of revolution；
(4) above-mentioned BiOCl colloid is centrifugated 10min with the speed of 4000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 10MPa, 35 DEG C of temperature, carbon dioxide flow 5m/s, dehydrated alcohol is replaced into liquid
Carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 10min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Embodiment 8：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOI)1- YNY, Y 0.25%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 40min, continue to be heated to 880 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 3mm, is 85m/s, temperature using flow velocity
For 100 DEG C of nitrogen continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 600r/min high-speed stirred2O3It is added in 75 DEG C of excessive HI, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 20% is added dropwise, stirs 30min, reduces revolving speed to 400r/min, continues to stir 40min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOI colloid for the slow-speed of revolution；
(4) above-mentioned BiOI colloid is centrifugated 15min with the speed of 5500r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 10MPa, 35 DEG C of temperature, carbon dioxide flow 8m/s, dehydrated alcohol is replaced into liquid
Carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOI gel；
(6) BiOI gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 15min, and reaction end can be obtained nitrogen-doped nanometer BiOI type light and urge
Agent.
Embodiment 9：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.35%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 5m/s into melt is protected
After temperature stirring 50min, continue to be heated to 860 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 1mm, is 60m/s, temperature using flow velocity
For 85 DEG C of argon gas continuous crushing superheated melt thread, ultra-fine bead is obtained, ultra-fine bead burns in oxygen, obtains liquid
Bi2O3；
(3) by liquid Bi under 700r/min high-speed stirred2O3It is added in 65 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 23% is added dropwise, stirs 40min, reduces revolving speed to 400r/min, continues to stir 28min, finally drop
To 100r/min, natural cooling cools down at this time, obtains BiOCl colloid for the slow-speed of revolution；
(4) above-mentioned BiOCl colloid is centrifugated 16min with the speed of 4000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8.5MPa, 35 DEG C of temperature, carbon dioxide flow 6m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 15min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Embodiment 10：
A kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOCl)1- YNY, Y 0.33%.
Preparation method includes the following steps：
(1) refined bismuth is heated to 300 DEG C of meltings and obtains melt, the continual nitrogen for being passed through 4m/s into melt is protected
After temperature stirring 35min, continue to be heated to 880 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by the diversion pipe that diameter is 4mm, is 100m/s, temperature using flow velocity
The air continuous crushing superheated melt thread that degree is 100 DEG C, obtains ultra-fine bead, ultra-fine bead burns in oxygen, obtains liquid
State Bi2O3；
(3) by liquid Bi under 600r/min high-speed stirred2O3It is added in 65 DEG C of excessive HCl, obtains clear solution
Afterwards, the ammonium hydroxide that mass concentration is 15-25% is added dropwise, stirs 35min, reduces revolving speed to 400r/min, continues to stir 20min, most
Revolving speed is reduced afterwards to 100r/min, and natural cooling cools down at this time, obtains BiOCl colloid；
(4) above-mentioned BiOCl colloid is centrifugated 10min with the speed of 4000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 10MPa, 35 DEG C of temperature, carbon dioxide flow 8m/s, dehydrated alcohol is replaced into liquid
Carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOCl gel；
(6) BiOCl gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma electric arc
Haptoreaction, carries out N doping reaction, reaction time 12min, and reaction end can be obtained nitrogen-doped nanometer BiOCl type light and urge
Agent.
Light-catalyzed reaction degradation experiment：
Nitrogen-doped nanometer BiOCl type photochemical catalyst and nano bismuth oxide, nanometer oxychloride prepared by the embodiment of the present invention 1
Bismuth carries out light-catalyzed reaction degradation property and compares, and concrete outcome is as shown in the following table 1, shown in table 2：
Table 1：
Reaction condition：Reaction carries out in crystal reaction tube, methylene blue concentration 6mg/L, nitrogen-doped nanometer BiOCl type light
Catalyst, nano bismuth oxide, nanometer bismuth oxychloride are 100mg, and suspension is made, adds H2O22ml, illumination reaction
40min。
Table 2：
Reaction condition：Reaction carries out in crystal reaction tube, methylene blue concentration 6mg/L, nitrogen-doped nanometer BiOCl type light
Catalyst, nano bismuth oxide, nanometer bismuth oxychloride are 100mg, and suspension is made, adds H2O22ml, illumination reaction, observation
Suspension color change.
According to the experimental results, the embodiment of the present invention has degradation time short, the high advantage of degradation rate.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that：It still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (9)
1. a kind of nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity, which is characterized in that molecular formula is (BiOX)1-YNY, X
For Cl, Br, I any one, Y 0.25-0.35%.
2. the preparation method of the nitrogen-doped nanometer BiOX type photochemical catalyst of high catalytic activity as described in claim 1, feature
It is, includes the following steps：
(1) refined bismuth is heated to 280-300 DEG C of melting and obtains melt, it is continual into melt to be passed through nitrogen, insulated and stirred
After 20-50min, continue to be heated to 860-950 DEG C to obtain superheated melt；
(2) superheated melt is entered in atomising device by diversion pipe, using atomization gas continuous crushing superheated melt thread, is obtained
To ultra-fine bead, ultra-fine bead burns in oxygen, obtains liquid Bi2O3；
(3) by liquid Bi under 600-800r/min high-speed stirred2O3It is added in 60-80 DEG C of excessive HX, obtains clear solution
Afterwards, ammonium hydroxide is added dropwise, stirs 20-40min, reduces revolving speed to 400r/min, continues to stir 20-40min, finally reduce revolving speed extremely
100r/min, natural cooling cools down at this time, obtains BiOX colloid；
(4) BiOX colloid is centrifugated 10-20min with the speed of 4000-6000r/min, the solid material being centrifuged is steamed
Distilled water and dehydrated alcohol respectively wash 3 times；
(5) under conditions of pressure 8-10MPa, 35 DEG C of temperature, carbon dioxide flow 5-10m/s, dehydrated alcohol is replaced into liquid
State carbon dioxide, after restoring normal pressure, after cooled to room temperature, 450 DEG C of calcining 150min obtain BiOX gel；
(6) BiOX gel is placed in reactor, under normal pressure equably with nonequilibrium state nitrogen direct-current plasma arc contacts
Reaction, carries out N doping reaction, reaction time 10-15min, and reaction terminates that nitrogen-doped nanometer BiOX type photocatalysis can be obtained
Agent.
3. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the nitrogen
Flow velocity be 2-5m/s.
4. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the water conservancy diversion
The diameter of pipe is 1-4mm.
5. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the atomization
Gas is air, nitrogen, any one in argon gas.
6. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the atomization
The flow velocity of gas is 60-100m/s.
7. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the atomization
The temperature of gas is 80-100 DEG C.
8. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the HX is
HCl, HBr, HI any one.
9. the preparation method of nitrogen-doped nanometer BiOX type photochemical catalyst as claimed in claim 2, which is characterized in that the ammonium hydroxide
Mass concentration is 15-25%.
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| CN111905808A (en) * | 2020-07-16 | 2020-11-10 | 兰东辉 | Graphene-based composite material and preparation method thereof |
| CN113457706A (en) * | 2021-06-23 | 2021-10-01 | 江苏大学 | Synthesis of N-BiOBr/CQDs/Fe by pollutant template element filling strategy3O4And applications thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111905808A (en) * | 2020-07-16 | 2020-11-10 | 兰东辉 | Graphene-based composite material and preparation method thereof |
| CN113457706A (en) * | 2021-06-23 | 2021-10-01 | 江苏大学 | Synthesis of N-BiOBr/CQDs/Fe by pollutant template element filling strategy3O4And applications thereof |
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